Textile material with an antistatic finish and process of making same



States Unite TEXTILE MATERIAL WITH AN ANTISTATIC FINISH AW PRQCES 9F MAKING SAD E No Drawing. Application August 31, 1951, Serial No. 244,739

13 Claims. (Cl. iii-138.8)

The present invention relates to the treatment of synthetic polymer textile materials, particularly unspun fibers composed Wholly or partly of fiber-forming synthetic polymers, and to the textil materials so produced.

It is one object or this invention to provide improved processes for treating synthetic polymer textile materials, particularly unspun fibers composed Wholly or partly of fiber-forming synthetic polymers, to render the textile materials more amenable to mechanical processing.

it is a further object of this invention to provide improved processes for treating synthetic polymer textile materials, particularly unspun fibers composed Wholly or partly of fiber-forming synthetic polymers, to provide such materials with a soft, anti-static finish or dressing.

it is a further object of this invention to provide synthetic polymer textile materials, particularly unspun fibers composed Wholly or partly of fiber-forming synthetic polymers, having a soft, anti-static finish or dressing.

Still further objects and advantages of this invention Will become apparent in the following description and the appended claims.

The objects of this invention are attained, in general, by applying a quaternary phosphonium salt to a synthetic polymer textile material. The amount of quaternary phosphonium salt applied may vary considerably but should be sufficient to minimize the formation of static electricity on such textile materials during the handling or manipulation of the textile materials.

The term textile materials as used in the specification and the appended claims is intended to-include undyed or dyed unspun fibers, yarns, continuous filaments or fabrics comprising at least 10% by Weight of a fiberforming synthetic polymer. The processes of this invention are particularly applicable to the treatment of unspun fibers comprising at least 10% by Weight of unspun staple fibers of a fiber-forming synthetic polymer to render such fibers amenable to spinning and to minimize the formation of static electricity on such fibers during the processing of such fibers preparatory to spinning the fibers into yarns. Accordingly, the treatment of such unspun fibers is preferred.

As examples of fiber-forming synthetic polymers which are included in the textile materials defined above may be mentioned the fiber-forming copolymers of vinyl chloride and vinyl acetate; the fiber-forming polymers of vinylidene chloride and copoiymers of a major proportion of vinylidene chloride and a minor proportion of an unsaturated compound copolymerizable therewith having the grouping CH2:C such as, for example, vinyl compounds including vinyl chloride; fiber-forming linear polyesters of glycols such as ethylene glycol and terephthalic acid; fiber-forming homopolymers of acrylonitrile and heteropolymers containing combined acrylonitrile such as, for example, heteropolymers of a major proportion of acrylonitrile and a minor proportion of an unsaturated organic compound copolymerizable therewith having the grouping CH2=C including such compounds as styrene, alkyl and halogen nuclear substituted styrene, vinyl Patented Nov. 27, 1956 chloride, alkyl acrylates such as methyl or ethyl acrylate, alkyl methacrylates such as methyl or ethyl methacrylates, vinyl pyridine, divinyl benzene and the like; and fiberforming linear polyamides such as, for example, polyhexamethylene-adipamide, polyhexamethylene-sebacamide and the fiber-forming linear polyamides described in United States Patent No. 2,071,250, No. 2,130,532 and No. 2,130,948. Mixtures of such fiber-forming synthetic polymers may also be used.

The processes of this invention are more particularly suitable for the treatment of upspun staple fibers containing at least 10% by weight of polyhexamethylene-adipamide staple fibers or staple fibers of polyacrylonitrile or fiber forming heteropolymers containing combined acrylonitrile, or mixtures of such staple fibers. Accordingly, the treatment of these specific staple fibers is preferred.

As examples of textile fibers, yarns or filaments which may be combined with the synthetic polymer materials to form the textile materials defined above may be mentioned fibers, yarns or continuous filaments of natural cellulose materials uch as cotton, linen, rarnie or the like, synthetic regenerated cellulose materials such as viscose rayon, cuprammonium rayon and saponificd cellulose acetate; natural or synthetic proteinaceous materials such as Wool, or animal fibers, casein, peanut protein and the like; and cellulose derivative materials such as cellulose esters derived from cellulose and an aliphatic acid as, for example, cellulose acetate, and Water-insoluble cellulose ethers. Mixtures of fibers, yarns, and continuous filaments of such materials may also be used with the fiberforming synthetic polymer materials.

The quaternary phosphonium salts may be applied to the textile materials defined above in various Ways. Thus, organic solvent solutions or aqueous solutions or dispersions of the quaternary phosphonium salts may be sprayed or dripped on the textile materials, or the textile materials may be immersed in such solutions or dispersions, or the textile materials, particularly in the case 01: yarns or filaments, may be passed over a roller coated with such solutions or dispersions. The particular method of application employed will vary depending on the form of the textile used Thus, in the case of unspun textile fibers, the fibers are usually treated by immersing them in or spraying them with the solutions or dispersions of the quaternary phosphonium salts, although such fibers may also be treated by a dripping process. In the case of yarns or filaments it is preferred to pass such materials over a roll which is coated with a solution or dispersion of the quaternary phosphonium salt, or by immersing the yarns or filaments in a solution or dispersion of such salt and then removing the excess solution or dispersion by squeezing or centrifuging, or by means of suction or compressed air. Fabrics are preferably treated by a padding operation in which the fabrics are first immersed in a solution or dispersion or" the quaternary phosphonium salt and then passed between squeeze rolls to remove excess solution or dispersion. Fabrics may, however, be treated by spraying, or they may be treated in conventional dyeing apparatus. For convenience of application it is preferred to use aqueous solutions or dispersions of Water-soluble quaternary phosphonium salts.

The term solution as used in the appended claims is intended'to include true solutions, stable colloidal solutions and stable dispersions since it is believed that in some instances the quaternary phosphonium salts are present in the liquid phase as a solute, colloid and as a disperse phase.

The solutions or dispersions of the quaternary phosphonium salts employed herein may comprise small amounts, say from about 0.01 to 5% by Weight of conventional textile assistants or adjuvants, as for example,

lubricantssuch as mineral oils, vegetable oils, sulfonated or sulfated mineral oils or vegetable oils, butyl stearate, mixtures of such materials, including oil-dispersible or water-dispersible' mixtures and the like; humectants such as sorbitol, glycen'ne and the like; dispersing agents such as 'sorbitol laurate and ethylene oxidealkyl mercaptan condensation products, in which the alkyl group contains at least 8 carbon atoms; monohydric compounds such as butyl alcohol, Z-ethoxyethanol diethylene glycol ethyl ether and the like; and wetting agents such as ammonium stearate.

Regardless of the mode of applying the solutions or dispersions 'of the quaternary phosphonium salts to the textile material, it is necessary to deposit on the textile material an amount of quaternary phosphonium salt sulficient' to minimize the formation of static electricity on such textile materials during subsequent processing operations. Usually the application of from about 0.01 to 5% by weight of the quaternary phosphonium salts, on the dry weight of the textile materials, will give satisfactory results. However, it is always possible to apply larger amounts of such salts, for example, up to by weight based on the dry weight of the textile material. Best results are obtained by applying from about 0.3 to 3% by weight of the quaternary phosphonium salt, based on the dry weight of textile materials, and such amounts are accordingly preferred.

In order to obtain the desired anti-static efiects on the treated textile materials it is essential that the textile material contain a continuous coating or deposit of the quaternary phosphonium salt on the surface of the m-a 'terial.

The above described amounts of quaternary phosphonium salts are applied to the textile materials by properly adjusting the concentration of the salt in the solution which is applied to the textile materials, or by adjusting the concentration ofsalt in the solution which is applied and then squeezing, centrifuging, sucking or blowing the excess solution from the textile materials. In general, a solution containingfrom about 0.01 to 10% by weight of the quaternary phosphonium salt will deposit the desired amounts of the salt within the ranges specified above, depending on the amount of pick up obtained.

After the textile materials have been treated a described above, they =are normally dried either by allowing the materials to dry at ordinary room temperatures or by heating the textile materials in a current of warm or 'hot air, for example, at temperatures of 110 to 200 F. This is the normal procedure in the treatment of unspun fibers, yarns or filaments and is usually the procedure followed in the treatment of fabrics.

By carrying out the processes described herein, it is possible to provide synthetic polymer textile materials, "as hereinbefore defined, having a finish which is soft and has anti-static properties, that is, the property of substantially preventing the build-up of static electric charges on the dry textile materials during manipulation or handling.

A further understanding of the processes and textile materials described herein will be obtained from the following specific examples which are intended to illustrate this invention, but not to limit the scope thereof, parts and percentages being by weight unless otherwise specified. 7

Example I Polyhexamethylene-adip-amide continuous filaments were immersed in a 2% water solution of benzyl tris (dimethylamino) phosphonium chloride and squeezed between pad rolls to obtain'a pickup of 80% of the solution, based on the dry filament Weight. The filaments were then air dried at a temperature of about 70 F., after which they were spun into plied yarns. The filaments did not accumulate static electric charges, whereas equivalent filaments which were not treated with the phosphonium salts accumulated a noticeable charge of static electricity during the spinning of the plied yarns.

4 Example II A woven fabric consisting of polyhexamethyleneadipamide filaments in the warp and filling, and having a static charge of 148 microamperes as measured on a Hayek static tester, was immersed in a 2% water solution of benzyl tris (dimethylamino) phosphonium chloride,

. after which it was passed between pad rolls to obtain a pick up of of the solution, based on the dry fabric The fabric was then air dried at a temperature weight. of F. The resulting fabric had a zero static charge as measured on a Hayek static tester as compared to the 148 microampere charge on the untreated fabric.

The Hayek static tester which is referred to in the foregoing example and which is also referred to in Example III is described in the American Dyestufi Reporter, volume 40, No. 5 (March 5,1951).

Example III A woven fabric consisting of yarns prepared entirely of staple fibers of a fiber-forming heteropolymer of acrylonitrile and 15% vinyl chloride, and having a static charge of 25 microamperes as measured on a Hayek static tester, was immersed in a 5% water solution of cetyl tris (dimethylamino) phosphonium bromide, after which it was passed between pad rolls to obtain a pick up of 70% of the solution, based on the dry weight of the fabric, and the fabric was then allowed to air dry at a temperature of 70 'F. The resulting fabric had a Zero static charge as measured on a Hayek static tester as compared to the '25 microampere charge on the untreated fabric.

Example IV T ning system. The textile fibers did not accumulate static cumulated a static charge which interfered considerably with the processing and spinning of the fibers.

electric charges during the processing and spinning operations, whereas an equivalent mixture of fibers which were not treated with the quaternary phosphonium salt ac- Example V Unspun staple fibers consisting of a fiber-forming heteropolymer of acrylonitrile and 5% vinyl pyrdried at a temperature of 75 F. and then processed into yarns in accordance with the American wool spinning system. The treated fibers did not accumulate static electric charges during the processing and spinning of the fibers, whereas identical fibers which had not been treated with the quaternary phosphonium salt accumulated electric charges which interfered appreciably with the processing and spinning of the fibers. I In addition to providing a soft, anti-static finish 0 linear polyamide textile materials as hereinbefore described, it has presently been found that the quaternary phosphonium salts also serve to improve the depth of dye shade on such textile materials when the materials are dyed with acid dyestufis or mordant acid dyestuffs in the presence of such quaternary phosphonium salts. In carrying out this embodiment of the invention it is possible to apply the quaternary phosphonium salt to the linear polyamide textile material prior to the dyeing operation for the quaternary phosphonium salt may be added to the dye bath in the concentrations hereinbefore specified. The dyeing operation is carried out by heating the dye bath at elevated temperatures, for example, above 150 F. and preferably at the boil, until the desired dye shade has been obtained, after which the dyed material is rinsed with water and dried. The dye bath may contain the common dye bath additives such as alkali metal salts, for example, sodium sulfate or sodium chloride to assist in exhausting the dye on the textile material. The following example serves to illustrate this embodiment of the present invention.

Example VI Filaments consisting of polyhexamethylene-adipamide Were immersed in an aqueous bath containing 4% Pontachrome Black TA (colour index number 203), 5% acetic acid /2% xylyl tris (dimethylamino) phosphonium bromide and glauber salt. The bath which was originally at a temperature of 100 F. was heated to a temperature of 190 F. After the bath was maintained at 190 F. for minutes 2% of concentrated sulfuric acid was added and this was repeated 20 minutes later. The bath was maintained at 190 F. for a total period of 60 minutes, after which the filaments were removed from the bath, rinsed in cold water and dried at 180 F. The resulting filaments had an excellent depth of dye shade in contrast to filaments dyed without the phosphonium salt, and also possessed a soft, anti-static finish.

A wide variety of quaternary phosphonium salts may be used in the processes of this invention, including the quaternary phosphonium chlorides, bromides, iodides, fluorides, sulfates, aliphatic monocarboxylates containing from 8 to 24 carbon atoms such as the stearates, oleates, palmitates and the like. The quaternary phosphonium aliphatic monocar'ooxylates are normally oil-soluble and Water-insoluble but are dispersible in water with the aid of dispersing agents. Such phosphonium carboxylates are readily prepared, for example, by reacting a water-soluble salt of an aliphatic monocarboxylic acid containing from 8 to 24 carbon atoms as, for example, sodium oleate or sodium stearate with a quaternary phosphonium halide. The quaternary phosphonium chlorides and bromides are particularly suitable because they are easily prepared and are preferred over the iodides, fluorides and other water-soluble phosphonium salts. A class of compounds which may be used are the class of compounds represented by the general formula:

where R is an alkyl radical containing from 6 to 24 carbon atoms, R represents alkyl radicals containing from 1 to 4 carbon atoms and X is a member selected from the class consisting of bromine, chlorine and iodine atoms and aliphatic monocarboxylate radicals containing 8 to 24 carbon atoms. This class of compounds includes cetyl trimethyl phosphonium chloride, bromide, or iodide, dodecyl trimethyl phosphonium bromide, octyl triethyl phosphonium bromide, cetyl trimethyl phosphonium stearate and the like.

Another class of quaternary phosphonium salts which may be used are compounds represented by the general formula:

where R is an aryl-alkyl radical, R is an alkyl radical containing from 1 to 4 carbon atoms and X is a member of the class consisting of chlorine, bromine and iodine 6 atoms and aliphatic monocarboxylate radicals containing 8 to 24 carbon atoms. This class of compounds includes benzyl trimethyl phosphonium bromide, chloride or iodide, benzyl triethyl phosphonium chloride or bromide and the like.

A class of compounds which are particularly suitable in the processes of this invention is the class of nitrogencontaining phosphonium compounds represented by the general formula:

where F. is an alkyl radical containing from 6 to 22 carbon atoms, R is an alkyl radical containing from 1 to 4 carbon atoms and X is a chlorine or bromine atom or an aliphatic monocarboxylate radical containing 8 to 24 carbon atoms. This class of compounds which may be designated alkyl tris (dialkylamino) phosphonium chlorides, bromides or aliphatic monoca-rboxylates, includes such compounds as cetyl tris (dimethylamino) phosphonium chloride or bromide, dodecyl tris (dimethylamino) phosphonium chloride or bromide, n-hexyl tris (dipropylamino) phosphonium chloride or bromide, cetyl tris (dimethylamino) phosphonium stearate and the like. The halides are obtained by reacting an alkyl bromide or chloride containing from 6 to 22 carbon atoms with a hexa-alkyl phosphorous triamide having the formula: P(NR2)3, where R has the significance described above. This reaction is normally carried out at a temperature between about and 250 C. until the corresponding phosphonium halide is formed. Further examples of such halides and methods of preparing them are set forth in the co-pending application Serial No. 239,175 of William T. Dye, ]r., filed July 28, 1951 and now abandoned.

A preferred class of quaternary phosphonium salts for use in the processes of this invention is the class of nitrogen-containing phosphonium compounds represented by the general formula:

where R and R are chlorine, bromine and hydrogen atoms or alkyl radicals containing from 1 to 5 carbon atoms, R represents an alkyl radical containing from 1 to 4 carbon atoms and X is a chlorine or bromine atom or an aliphatic monocarboxylate radical containing 8 to 24 carbon atoms. As examples of this class of compounds may be mentioned benzyl tris (dimethylamino) phosphonium chloride or bromide, benzyl tris (diethylamino) phosphonium chloride or bromide, 4-ethyl benzyl tris (dimethylamino) phosphonium chloride or bromide, 2-chlorobenzyl tris (di-isopropylamino) phosphonium chloride or bromide, 3-bromobenzyl tris (diethylamino) phosphonium chloride or bromide, benzyl tris (dimethylamino) phosphonium stearate and the like. The benzyl tris (dimethylamino) phosphonium chloride and bromide are easy to prepare, and give excellent results. Accordingly, such compounds are preferred.

The halides of the class of compounds described immediately above are prepared, in general, by reacting the corresponding benzyl halide with a hexa-alkylphosphorous triamide in which the alkyl group contains from 1 to 4 carbon atoms. This reaction may be carried out at normal or elevated temperatures in the presence or absence of solvents or diluents. Further examples of this class of compounds and methods for preparing such compounds are given in the co-pending application Serial No. 223,449 of William T. Dye, In, filed April 27, 1951, and now abandoned.

A wide variety of acid dyestuffs or mordant acid dyestuflFs may be used instead of the dyestufi employed in Example VI. As examples of such'dyestutfs may be mentioned the following:

Name of dyestuff: Colour index number Pontachrome Brown G 238 Kiton Fast Yellow 3G"; 639 Hudson Chrome Red B 216 Formyl Violet S4B 698 Metamine Fast Acid Red N 636 Chromaven Brilliant Blue B 720 Chromoxane Cyanine RA 722 Xylene Milling Blue BL 833 Wool Orange A 151 Other suitable acid and mordant acid dyestufis will be apparent to those skilled in the art.

Various modifications and changes may be made in the processes and textile products described herein as will be apparent to those skilled in the art to which this invention appertains without departing from the spirit and intent of the invention described herein. It is accordingly understood that it is not intended to limit this invention except by the scope of the appended claims.

What is claimed is:

l. Textile materials consisting of textile fibers, of which at least 10% by weight are fiber-forming synthetic polymer fibers, and a quaternary phosphonium salt distributed continuously on the surface of said textile fibers, said salt being present in said materials in an amount sufficient to provide an anti-static finish and having the general formula:

where R and R are selected from the group consisting of chlorine, bromine and hydrogen atoms and alkyl radi cals containing from 1 to 5 carbon atoms, R" is an alkyl radical containing from 1 to 4 carbon atoms and X is selected from the group consisting of chlorine and bromine atoms and aliphatic monocarboxylate radicals containing 8 to 24 carbon atoms.

2. Textile materials according to claim 1, but further characterized in that the materials consist of yarns.

3. Unspun textile fibers consisting of said fibers, of which at least 10% by weight are unspun fiber-forming synthetic polymer fibers, and a quaternary phosphonium salt distributed continuously on the surface of said fibers, said salt being present on the fibers in an amount suificient to provide an anti-static finish and having the geneeral formula:

Dom-a bum" where R and R. are selected from the group consisting of chlorine, bromine and hydrogen atoms and alkyl radicals containing from 1 to 5 carbon atoms, R" is an alkyl radical containing from 1 to 4 carbon atoms and X is selected from the group consisting of chlorine and bromine atoms and aliphatic monocarboxylate radicals containing 8 to 24 carbon atoms.

4. Unspun textile fibers consisting of said fibers, of which at least 10% by weight are unspun fiber-forming synthetic polymer fibers, and benzyl tris (dimethylamino) phosphonium chloride distributed continuously on the surface of said fibers, said chloride being present on the fibers in anamount sufiicient to provide an anti-static finish.

5. A process of treating textile materials comprising at least 10% by weight of a fiber-forming synthetic polymer. which comprises applying to said textile materials a solution consisting of a quaternary phosphonium salt having the general formula:

where R and R are selected from the group consistingof chlorine, bromine and hydrogen atoms and alkyl radicals containing from 1 to 5 carbon atoms, R" is an alkyl radical containing from 1 to 4 carbon atoms and X is selected from the group consisting of chlorine and bromine atoms and aliphatic monocarboxylate radicals containing 8 to 24 carbon atoms, and a solvent for said salt, said salt being supplied in an amount sufiicient to provide an anti-static finish on said textile materials.

6. A process as in claim 5, but further characterized in that said textile materials are textile yarns.

7. A process of treating unspun textile fibers compris-- ing at least 10% by weight of staple fibers of a fiberiorming synthetic polymer to render said fibers more amenable to processing prior to spinning which comprises applying to said fibers a solution consisting of a quaternary phosphonium salt having the general formula:

where R and R are selected from the group consisting of chlorine, bromine and hydrogen atoms and alkyl radicals containing from 1 to 5 carbon atoms, R" is an alkyl radical containing from 1 to 4 carbon atoms and X is selected from the group consisting of chlorine and bromine atoms and aliphatic monocarboxylate radicals containing 8 to 24 carbon atoms, and a solvent for said salt, said salt being supplied in an amount sufl'icient to provide an anti-static finish on said fibers and drying said fibers.

'8.'A process of treating unspun textile fibers comprising at least 10% by weight of staple fibers of a fiberforming synthetic polymer to render said fibers more amenable to processing prior to spinning which comprises applying to said fibers a solution consisting of benzyl tris (dimethylamino) phosphonium chloride and a solvent therefor, said chloride being supplied in an amount sufiicient to provide an anti-static finish on said 9. A process of treating unspun textile fibers comprising at least 10% by weight of staple fibers of a fiberforming synthetic polymer to render said fibers more amenable to processing prior to spinning which comprises applying to said fibers a solution consisting of benzyl tris (dimethylamino) phosphonium bromide and a solvent therefor, said bromide being supplied in an amount sufiicient to provide an anti-static finish on said fibers.

10. A process of treating unspun textile fibers comprising at least 10% by weight of staple fibers of a fiberforming synthetic polymer to render said fiber more amenable to processing prior to spinning which comprises applying to said fibers an aqueous solution consisting of water and a water-soluble quaternary phosphonium salt having the general formula:

R X NR3 where R and R are selected from the group consisting of chlorine, bromine and hydrogen atoms and alkyl radicals containing from 1 to 5 carbon atoms, R" is an alkyl radical containing from .1 to 4 carbon atoms and X is selected from the group consisting of chlorine and bromine atoms and aliphatic monocarboxylate radicals containing 8 to 24 carbon atoms, said solution being supplied in an amount sufiicient to provide from 0.01

to 10% by weight of said salt, based on the dry weight of said fibers,- and then drying said fibers.

A process as inclaim 10, but further characterized in that the textile fibers comprise at least 10% by weight of staple fibers of polyhexarnethylene-adiparnide.

12. A process as in claim 10, but further characterized in that the textile fibers comprise at least 10% by Weight of staple fibers of polyacrylonitrile.

13. A process as in claim 10, but further characterized in that the textile fibers comprise at least 10% by Weight of staple fibers of a fiber-forming heteropolymer containing combined acrylonitrile.

References Cited in the file of this patent UNITED STATES PATENTS 10 2,492,394 Olpin et a1 Dec. 27, 1948 2,543,539 WiZOn Feb. 27, 1951 2,563,506 Werntz Aug. 7, I951 FOREIGN PATENTS 437,274 Great Britain of 1935 OTHER REFERENCES Michaelis et al.: Ber deut Chem, vol. 28 (1895), pp. 2205-2211.

Michaelis: Liebigs Annalen, vol. 326 (1903), pp. 169 to 171.

Kosolapofi: Organophosphorous Compounds (Wiley and Sons, Inc.), 1950, pp. 325, 327 and 332.

Jour. Society Dyers and Colorists for May, 1945, pages 122125.

Amer. Dyes. Reporter for Oct. 19, 1936, pages 561- 565. 

5. A PROCESS OF TREATING TEXTILE MATERIALS COMPRISING AT LEAST 10% BY WEIGHT OF A FIBER-FORMING SYNTHETIC POLYMER WHICH COMPRISES APPLYING TO SAID TEXTILE MATERIALS A SOLUTION CONSISTING OF A QUATERNARY PHOSPHONIUM SALT HAVING THE GENERAL FORMULA: 